Coating compositions comprising metallic dust



United States Patent fi ice Patented Aug. 14, 1956 COATING .GOMBOSITION S COMPRISING METALLIC DUST.

Harry Tommie-n. Daytouyohimassignor to 'Midland Chemical: Corporation; a icorporationrol: Deiaware.

No Drawing. Application May 11, 1953, Seriah Nov 354,373

This-invention relatesvto new -compositions comprising alkyd "rcsinsuand metallicadustuandi adapted: for use as protective coating materials and as molding compositions.

Ql'i6';0bi6t"0f this-invention isi-to provide new coma positions which can be applied to metal surfaces orrthe liker.forrprotective, anti-corrosionpurposes and polymeri-zedor) cured after deposition on the base.-

Another'zobject' is to provide compositionswwhich; after deposition and hardening. thereof on. a.-metalxsurface-:or base, provides thevlatter: with a hard, durable protective filmorcoating'comprisingmetallic particles imbedded inianthermoset resin matrix. A further object is. to pro, vidercompositionswhich canbemolded. intoshaped objects having a-metallic ellect:

Theseiand other objects are accomplishedby providing new polymerizable: coatings compositions comprising: i a liquid polyester resin, .a polymerizable: vinyl-substituted heterocyclic tertiary amine, and metallic particles.

The: polyester component: of" the; composition -is :an alkyd resin,..or; morewproperly, an alkyduresinwprecon-i' densate, the term alkyd resin asused herein includingmm modified. and modified. polyhydric alcohol polyesters of alpha: unsaturated alpha beta-polycarboxylie. acidsn. Typical Ofwthe polyhydric alcolhols used in makingsuch resins are ethylene glycol; di-, tlli", and tetra-ethylenewglyeol propylene glycol; dipropyleue glycoL. trimethy-lene glycol,. glycerol and pentaerythritol. Examples of the alpha-unsaturatedalphaebeta polycarboxylic. acids are maleic, fumaric; chlormaleic chlorofumaric, citraconic, methylethyl maleic, diethyl-maleic, .chloromethyl .maleic and mesaconic acids. In imakinglthe-unmodified alkyd or polyester resins, one ormore-of theiforegoing alcohols is heated: with -a roughly equivalent proportion of oneor more :of the.acids,-their anhydrides, .or-compounds which liberatethe acids fora timesuificient-toreifect con'f densation tothe stage, at which the condensate occurs as a liquid, resinous polyester. In: making; the modified alkyd'resins, a part, or evennearly all, eithe-unsaturated polycarboxylic acid may be substituted, by saturated monoor polycarboxyli'cacid,-.,such as'suceinic, adipic, phthalic, sebacic-or IZ-hydroxystearicacide. Monobasic acids having fron -20. car-bons. .m;ay-- be preferred These acids may be-mixed-fatty acids derived. from- .vegetable oils or theindividual acids present therein. When desired,-the vegetable oils themselves maybe incorporated byconventionalmethods; e; g.', by-the. sorcalled alcor holysis method; As examples of vegetable oils may be mentioned linseed oil, perillaoil, soybean. oil, castor oil, dehydrated castonoil, palm. kernel oil, ,cocoanut oil and-the like.- Such resins,;- both of the unmodified and modifiedtype are:known in. the art andavailable commerically under a variety of: trade-names.-

The alkyd :or polyester resin is made up of repeating groupings; containing. alcohol and-acid. units andmay havea molecular weight asmeasuredi by ;meacid, value oft-he. resin; otover 500, molecularweights, of, 1 000.or over b saae er ly pr f e The melecular weight should :be. such that the liquid resin is capable :of :being; blended uniformlywiththe vinyksubs-tituted hetero.-= cyclic tertiary amine. in conventional-type mixingsap-i paratus.

Examples of .thevinyl-substituted heterocyclic; .terti'any amines which (may; be used-.include-the: vinyl pyridines; for instance, 2-ivinylpyridinep. S-vinyl-fimethylpypidine; 5-ethyl-2-vinylpyridine,. and. :the- .vinylpyridines and; thein alkyl nuolearly substituted derivitatives generally iniwhicha the alkyl radicals contain from l to 4 carbon: at0m$, .th vinylimidazoles; thevinylquinolines, .ther-yinyl-isoquino-j lines, the vinylthiazoles, the -vinyloxazoles-,i.the vinyl benZo-oxazoles, etc;

The particulate metal may beizinc; aluminum; titanium; magnesium, zirconium or lithiumparticles-shaving a di-. ameter between about0=5 and 31} microns:(sub=sieve x1e: termination) The compositions ofthe: invention :may :be preparednby mixing or blending the. polymerizablm. preferably IHQIlQr meric, vinyl-substituted heterocyclic tertiary amine with: the-liquid, resinous polyester, and thenadding ;the:metal.-l lic particles to the mixture, withnstirrings The-metallic particlestenduto remain suspended in thevresinous liquid bleudii.

In: these compositions,- llhfiv vinyl-substituted:hetero-- cyclicitertiar-y aminef unct-ions; initially, as a. diluent for; the polyesterl; Qn' heating. of themix. tocuring. tempera ture,-.the. amine :serves. vas :a tcross-linking agent for the polyester molecules: t0.:form'. a.-.web;like1 structure-. The curring, or thardening to thermosetteondition with; .simul-i taneous cross-.1inking- -of -the polyester molecules by; the vinyl-substituted amine. and polymerization of theulatter are best'accomplished: :lIl-alih61PIl6SfiflC6uOf acatalyse, A latent catalyst may beincorporatedin .-the mix during initial. blending, or the catalystimay be mixemwithgithe blend. immediately prior tousev thereof." Gatalysts which may; be; added to the composition-include :thEzOl'r? ganicperoxides such as benzoyl iperoxide; ,succinic per oxide; and especially; those. peroxides madeefrom fatty acids. having; from 10 to: 20; carbons i atom s,-, including lauroyl, 'stearoyl, and the peroxides; made. from vegetable oil acidssuch as coeoanutuoil.peroxides, Alcohol peroxides such as --tertiary butyl hydroperoxide andtiterpene oxides,- e.- g., ascaridole-may also be used.=. Normally; the, catalyst-may beusednin small amountsioflfronu .l l to, about 12%: of: the composition; by weight-..

Ifv the composition is tobe storedifor long time periods, it a is generally desirable to include. a. polymerizatiou =inhibitor with. it. Guaiacol; paraquinone paratertiar y butylaleohol;v hydroquino-ne; ortho-trinitroq; phenols and the: like are: suitable-inhibitors and: may; bewusedh in amounts between 0.2% to 1.0% byeweight'-of-.the:compo1 sitioni to inhibit or retard polymerization for-substantial perio dsof time;

The relative proportions of the polyester.andtvinyl-sub; stitu'ted heterocyclic tertiary amine may be rather widely varied and may be such. thanzthezblend comprises from 5 to 50 parts of the vinyl-substituted heterocyclic tertiary amine, .e. .g., a vvinylpyridine,.. sueh..as.2mirrylpyridiue or 5-vinyl-2-methylpyridine for eachlOO parts of the poly: estert The amountbimetallic dust used i111 theicempor sitionsmay range. from. abouLS lbs; to. lat-15s. .thereof per gallon of the blend. of polyester. and.amine,.these am un-tsbeing illustrative and. subject to selection and variation dependingon. the purposev for whichithe. com: positionis. intended and the efi'ect, to, be, achieved. When the composition is. to :be used'as a-protective coati'rig, a comparatively heavy concentration ofth'e metallic dust generally will be found, desirable.

Preferred compositions of the. iriventi-onare those which comprise the vinylsubstituted'heterocyclic tertiary amine and a resinous l-iquidpolyester'obtainedfrom the glycol;

e. g., propylene glycol and a mixture of an unsaturated dicarboxylic acid and a saturated dicarboxylic acid or the corresponding acid anhydrides. Typical is a mixture of maleic and phthalic acids, of maleic and phthalic anhydrides, or of maleic and tetrahydro phthalic anhydrides. Particularly preferred may be the polyesters obtained from mixtures of the saturated and unsaturated acids (or their anhydrides) in which the molecular ratio of saturated acid to unsaturated acid is not greater than 60:40. The mixtures may desirably comprise the acids (or anhydrides) in such proportions that the mole ratio of saturated acid to unsaturated acid is :90, :75 or 50:50. Polyesters formed from mixed saturated and unsaturated acids in which the saturated acid is phthalic acid (or the anhydride) are especially useful.

The polyester of the composition may be one which has been modified by including with the polyes'tenforming constituents an alcohol having a terminal OHz C group, including allyl alcohol and others of that class having from 3-10 carbon atoms. This includes methallyl alcohol, methyl vinyl carbinol, allyl ethyl alcohol, monoallyl and monomethallyl ethers of ethylene glycol and the like. Such modified polyesters are known and contain, in addition to the acid and polyhydric alcohol, residues of the unsaturated alcohol.

The polyester may also be one produced in the presence of a monohydric aliphatic alcohol such as l-bu-tanol, and other saturated lower aliphatic alcohols having straight or branched chains, particularly alcohols having 3-6 carbon atoms such as propanol, l-pentanol, 2-methyll-butanol, 2-pentanol, 2-methyl-2-butanol, 2-propanol, 2-butanol, 2-methyl-2-propanol and the like. The final polyester may, therefore, also contain residues of the saturated monohydric alcohol, preferably in an amount up to 1-10% of the total ester linkages.

One of the distinguishing features of the blends of this invention is that the vinyl-substituted heterocyclic tertiary amines are strongly receptive of the acid dye stufis which permits coloring of the blend as a whole by such dyes as a result of the occurrence of the vinylsubstituted tertiary amine homogeneously throughout the blend, and without the addition of dyes to the blend during mixing thereof. Various dyes and pigments may be incorporated, if desired, however.

It is to be noted that although the polyester may be prepared by reacting substantially equivalent parts of the polyhydric alcohol and polycarboxylic acid, variations in the properties of the polyesters may be achieved not only by conducting the esterification reaction in the presence of unsaturated allyl-type alcohols and/ or saturated monohydric alcohols, but also by variations in the relative proportions of the primary reactants, and particularly by selecting those reactants so that there is a slight preponderance of either the polycarboxylic acid or the polyhydric alcohol.

The following examples will illustrate specific embodiments of the invention, but are not to be considered as limiting its scope.

Example I A modified unsaturated resinous polyester resin is prepared by heating a mixture of 0.5 mol. (49 parts) maleic anhydride, 0.5 mol. (74 parts) phthalic anhydride and 1.2 mol. (92 parts) of propyleneglycol to 190 C. until a clear resinous liquid is obtained.

A sufficient amount of monometric Z-vinylpyridine is mixed, at room temperature, with the resinous polyester to obtain a mass comprising, on a weight basis, the equivalent of 40 parts of the vinylpyridine per each 100 parts of polyester.

Zinc dust is added slowly to the resinous liquid composition, with stirring, until a smooth suspension containobtained.

4 Example 11 An unmodified polyester is prepared by heating together equimolecular proportions of triethylene glycol and maleic acid until a partial condensate having the form of a resinous liquid is obtained.

The polyester is mixed, at room temperature, with a sufiicient amount of 5-vinyl2-methylpyridine per 100 parts of the polyester.

Zinc dust is added, with stirring and at a slow rate, until a suspension of 12 lbs. of the dust per gallon of the resinous liquid is obtained.

Example III A modified resinous polyester is prepared by heating mixture of ingredients as in Example I. The resin is blended with 2-vinylpyridine containing 1% by weight of hydroquinine, to obtain a homogeneous mix containing 30 parts of the vinylpyridine per 100 parts of polyester.

Zinc dust is then stirred in slowly until the suspension contains 12 lbs. of the dust per gallon of the resinous blend.

Small amounts of a catalyst, as described hereinabove, are added to the compositions, which are then coated onto a metal base to be protected against corrosion and hardened to infusible condition. The hardening may be effected at room temperature but is preferably expedited by the use of elevated temperatures which may range from 50 C. to 200 C., or the compositions are introduced into molds and heated to curing temperature in the molds. In molding the compositions, the curing or hardening may be carried out under atmospheric pressure or at higher pressures, such as from 0.5 lbs/sq. in. above atmospheric to 20 lbs/sq. in. (gauge), or even at pressures up to 300-500 lbs/sq. in.

The compositions may be molded in various ways, as for example by pouring into molds formed of wood, rubber, metal, plaster, concrete, etc. and in order to avoid sticking to the mold, the mold surfaces contacted by the composition may be protected with a mold lubricant such as zinc stearate or a natural or synthetic was, or such lubricants may be included in the composition.

Although the invention has been exemplified in terms of the polymerizable compositions containing zine dust, particulate metals other than zinc may be mixed with or suspended in the polymerizable composition, as has been mentioned hereinabove. Of special interest are such compositions containing aluminum flake.

These compositions have many advantages in the coating arts. The resin, after thermosetting thereof, adheres tenaciously to a metal base and serves as a hard but flexible anchor for the particulate metals so that the protected metal base may be subjected to flexing stress without disturbing the bond between it and the resin and particulate metal. The resin functions as a sealer for the metal particles.

The proportions of polymerizable alkyd and vinylsubstituted heterocyclic tertiaryamine may be selected so that the very finely divided metal particles, in the quantities mentioned herein or in larger quantities, remain substantially uniformly suspended therein and the composition is sprayable and can be applied to serve, for example, as an aluminum paint. Very finely divided pigments may also be suspended in the vehicle to provide a sprayable thermosettable composition which may be used as a flexible, sprayable one-coat protective and coloring coating composition for various metal substrates which, after application of the composition, may be moved through a baking zone for hardening the resin. This offers the extremely important advantage that any rusting resulting from scratches or abrasions is localized and does not tend to spread because the scratch is surrounded to the base with the resin. Various over-coatings may 5 be applied to the base carrying the coating compositions of the invention, if desired.

It will be understood that while there have been described herein certain specific embodiments of this invention, it is not intended thereby to have it limited to or circumscribed by the specific details given in view of the fact that this invention is susceptible of various modifications and changes which come within the spirit and scope of this disclosure.

I claim:

1. A sprayable, liquid, rustproofing coating composition consisting essentially of a polymerizable blend of (1) a liquid, potentially thermosetting component which consists essentially of a reaction product of an alphaunsaturated-alpha, beta-dicarboxylic acid and a polyhydric alcohol, with (2) from 5 to 50 parts by weight, per 100 parts of said liquid reaction product, of substantially monomeric 2-vinylpyridine, the liquid blend containing, per gallon thereof, from 5 to 18 lbs. of particles of a metal selected from the group consisting of zinc, alumi- References Cited in the file of this patent UNITED STATES PATENTS 2,576,392 Downes Nov. 27, 1951 2,600,457 Wynstra June 17, 1952 2,642,404 Pike June 16, 1953 2,645,626 Nordlander July 14, 1953 2,664,413 Parker Dec. 29, 1953 

1. A SPRAYABLE, LIQUID, RUSTPROOFING COATING COMPOSITION CONSISTING ESSENTIALLY OF A POLYMERIZABLE BLEND OF (1) A LIQUID, POTENTIALLY THERMOSETTING COMPONENT WHICH CONSISTS ESSENTIALLY OF A REACTION PRODUCT OF AN ALPHAUNSATURATED-ALPHA, BETA-DICARBOXYLIC ACID AND A POLYHYDRIC ALCOHOL, WITH (2) FROM 5 TO 50 PARTS BY WEIGHT, PER 100 PARTS OF SAID LIQUID REACTION PRODUCT, OF SUBSTANTIALLY MONOMERIC 2-VINYLPYDINE, THE LIQUID BLEND CONTAINING, PER GALLON THEREOF, FROM 5 TO 18 LBS. OF PARTICLES, OF A METAL SELECTED FROM THE GROUP CONSISTING OF ZINC, ALUMINUM, TITANIUM, MAGNESIUM, ZIRCONIUM AND LITHIUM HAVING A DIAMETER BETWEEN ABOUT 0.5 AND 3.0 MICRONS. 